Aromatic C–H amination in hexafluoroisopropanol

D’Amato, Erica M.; Börgel, Jonas; Ritter, Tobias

doi:10.1039/c8sc04966a

Cited by 85 publications

(62 citation statements)

References 45 publications

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“…Toward this endeavour our group and others have been working on iron catalyzed aminofunctionalization of alkenes [76–82] using hydroxylamine derived reagents. Additionally, we and others reported aromatic C−H amination reactions [83–87] through the use of similar reagents. The versatile reactivity of these iron catalyzed reactions of hydroxylamine derivatives in hydrocarbon functionalization reactions prompted us to investigate their reactivity in heteroatom amination reactions.…”

Section: Introductionmentioning

confidence: 79%

Hydroxylamine‐Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron‐Catalyzed Preparation of Unprotected Sulfinamides from Thiols

2020

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An iron catalyzed reaction for the selective transformation of thiols (‐SH) to sulfinamides (‐SONH2) by a direct transfer of ‐O and free ‐NH2 groups has been developed. The reaction operates under mild conditions using a bench stable hydroxylamine derived reagent, exhibits broad functional group tolerance, is scalable and proceeds without the use of any precious metal catalyst or additional oxidant. This novel, practical reaction leads to the formation of two distinct new bonds (S=O and S−N) in a single step to chemoselectively form valuable, unprotected sulfinamide products. Preliminary mechanistic studies implicate the role of the alcoholic solvent as an oxygen atom donor.

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Section: Introductionmentioning

confidence: 79%

Hydroxylamine‐Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron‐Catalyzed Preparation of Unprotected Sulfinamides from Thiols

2020

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“…The reaction requires the presence of hexafluoroisopropanol (HFIP) as an additive, a reaction medium with high polarity known to stabilize polar intermediates such as radicals [127][128][129]. The authors propose a mechanism based on the oxidation of the sulfinate by the T 1 state of 4,4′dimethoxybenzophenone forming the trifluoromethyl radical (vide supra) and a ketyl radical which deprotonates the acidic HFIP.…”

Section: Wang and Co-workers Discovered That Eosin Y Can Act As A P Hmentioning

confidence: 99%

Pushing the boundaries of C–H bond functionalization chemistry using flow technology

2020

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C-H functionalization chemistry is one of the most vibrant research areas within synthetic organic chemistry. While most researchers focus on the development of small-scale batch-type transformations, more recently such transformations have been carried out in flow reactors to explore new chemical space, to boost reactivity or to enable scalability of this important reaction class. Herein, an up-to-date overview of C-H bond functionalization reactions carried out in continuous-flow microreactors is presented. A comprehensive overview of reactions which establish the formal conversion of a C-H bond into carbon-carbon or carbonheteroatom bonds is provided; this includes metal-assisted C-H bond cleavages, hydrogen atom transfer reactions and C-H bond functionalizations which involve an S E-type process to aromatic or olefinic systems. Particular focus is devoted to showcase the advantages of flow processing to enhance C-H bond functionalization chemistry. Consequently, it is our hope that this review will serve as a guide to inspire researchers to push the boundaries of C-H functionalization chemistry using flow technology.

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“…Ritter and co-workers have reported a Fe-catalysed aromatic C-H amination, using [MsO-NH 3 ](OTf) as nitrogen source, for the synthesis of unprotected anilines (Scheme 6b). 15 The versatility of this methodology is attributed to the use of HFIP. The formation of a HFIP-triflate hydrogen bond, supported experimentally, enhances the reactivity of [MsO-NH 3 ](OTf) as oxidant.…”

Section: Hfip and Tfe: Super Polar Super H-bond Donorsmentioning

confidence: 99%

Emerging unconventional organic solvents for C–H bond and related functionalization reactions

Sanjosé‐Orduna

Patureau

et al. 2020

Chem. Soc. Rev.

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Aromatic C–H amination in hexafluoroisopropanol

Abstract: We report direct amination of electron-poor arenes and evaluate the crucial factors for the enhanced reactivity in hexafluoroisopropanol.

Cited by 85 publications

References 45 publications

Hydroxylamine‐Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron‐Catalyzed Preparation of Unprotected Sulfinamides from Thiols

Hydroxylamine‐Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron‐Catalyzed Preparation of Unprotected Sulfinamides from Thiols

Pushing the boundaries of C–H bond functionalization chemistry using flow technology

Emerging unconventional organic solvents for C–H bond and related functionalization reactions

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